A 7 ______B7_ 五、發明説明（1 ) 本發明係關於從由含合氧基（ = 〇)化合物，其中可 視需要再含可還原的基團，製造一級及/或二級胺之方法 ，該方法係使含合氧基化合物亞胺化且氫化亞胺化反應的 產物，本發明較宜從醛類與酮類製造一級單-及二胺類且 尤其是從異佛爾酮睛（=3_氰基一 3，5，5-三甲基 環己酮）製造異佛爾酮二胺（ = 3—胺基甲基一 3，5， 5 —三甲基環己胺）。 已知可使用氨或單焼基胺及氫氣經由還原性胺化反應 ，可將含合氧基化合物例如酮類與醛類轉化成一級及/或 二級胺類，此反應可在單一觸媒存在下進行，也就是說可 催化亞胺化反應與隨後氫化反應的觸媒，或在兩種觸媒存 在下進行，其中第一種催化亞胺化反應且第二種催化氫化 反應，在這些情形下，其中單階段方法使用單一觸媒導致 不滿意的的產量及/或不要的二級產物，例如直接氫化含 合氧基化合物而可得到的一磁醇，在二階段下進行還原性 胺化反應較爲有利，單階段方法（參見例如EP — A 〇 6 5 9 734)及二階段方法（參見例如EP_B 〇 經濟部中央標準局員工消費合作社印製 (請先閱讀背面.之注意事項再填寫本頁} 0 4 2 1 1 9 )都已知用於從異佛爾酮睛製造異佛爾酮二 胺，因爲希望在盡可能經濟及高純度下得到異佛爾酮二胺 作爲環氧樹脂硬化劑及作爲原料供製造異佛爾酮二異氰酸 鹽，其中需要有進一步改進的方法。 根據EP 0 042 119，使用一種銨形式的無 機或有機離子交換劑作爲亞胺化觸媒，供轉化反應相同屬 性型態的異佛爾酮腈成爲異佛爾酮二胺，在此文件中揭示 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ 一 4 一 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（2 ) 的亞胺化觸媒的缺點是，其中只有有機離子交換劑經證實 ，本身有熱及視需要的機械敏性》 爲了補救上述的缺點，在EP 〇 449 089中 提議使用酸性金屬氧化物，尤其是A 1 203、 T i 02、 S i 0 2及Z r 0 2作爲亞胺化觸媒且在兩個分開的反應腔 內進行反應，在2 0至15 0°C及1 5至2 0 0巴下進行 亞胺化，且在6 0至15 0 °C及5 0至3 0 0巴下進行氫 化，複製此方法發現形成非常大量的羥基胺類，也就是異 佛爾酮胺基醇（ = 3—胺基甲基_.3，5 ，5_三甲基環 己醇）的順式與反式異構物，因此需要竭力地完成純化步 驟。 當根據DE專利申請案195 40 191. 3使用 特殊的鈷氫化觸媒（雷內型態）製造異佛爾酮二胺時，證 明需要額外使用亞胺化觸媒以便使羥基胺類及其他不要的 二級產物降至最少，當使用結合亞胺化觸媒與鈷氫化觸媒 的觸媒降低亞胺基及睛基時，可得到非常良好的產量及高 純度的異佛爾酮二胺。 EP — A 〇 6 2 3 585也揭示二階段的方法供 還原性胺化酮類例如異佛爾酮睛，亞胺化觸媒爲活性碳， 氫化觸媒爲含鹼土金屬碳酸鹽及/或氧化鑭的鈷觸媒，從 實例說明的活性碳用量，發現觸媒的量相對於轉化的（ 97. 7%)異佛爾酮睛相當高，此導致髙反應器成本， 此方法的其他缺點是不完全的轉化及高壓° 根據DE — A 44 2 6 472即使當使用載體上 本紙張尺度適用中國國家標準（CNS ) A4規格（：210X297公釐） (請先閱讀背面乏注意事項再填寫本頁)A 7 ______B7_ 5. Description of the invention (1) The present invention relates to a method for producing a primary and / or secondary amine from a compound containing a oxy group (= 〇), which may further include a reducible group, if necessary. It is the product of the imidization and hydroimidization reaction of the oxygen-containing compound. The present invention is more suitable for the production of primary mono- and diamines from aldehydes and ketones, and especially from isophorone (= 3_ Cyano-3,5,5-trimethylcyclohexanone) makes isophorone diamine (= 3-aminomethyl-3,5,5-trimethylcyclohexylamine). It is known that ammonia or monofluorenylamine and hydrogen can be used to reduce the amination reaction by using a reductive amination reaction to convert primary oxygen-containing compounds such as ketones and aldehydes into primary and / or secondary amines. This reaction can be performed in a single catalyst. It is carried out in the presence of catalysts that can catalyze imidization and subsequent hydrogenation, or in the presence of two catalysts, the first of which catalyzes the imidization and the second of which catalyzes the hydrogenation. In some cases, a single-stage process using a single catalyst results in unsatisfactory yields and / or unwanted secondary products, such as a monoalcohol obtained by directly hydrogenating an oxygen-containing compound, and a reducing amine is carried out in a two-stage process The chemical reaction is more favorable, the single-stage method (see, for example, EP — A 〇 6 5 9 734) and the two-stage method (see, for example, EP_B 〇 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back.) Fill out this page} 0 4 2 1 1 9) are all known for the production of isophorone diamine from isophorone eyes because it is desired to obtain isophorone diamine as an epoxy in as economical and high purity as possible Resin hardener and For the production of isophorone diisocyanate as a raw material, there is a need for a further improved method. According to EP 0 042 119, an inorganic or organic ion exchanger in the form of ammonium is used as the imidization catalyst for the same conversion reaction The property type of isophoronenitrile becomes isophoronediamine. In this document, it is revealed that the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ 1-4. Consumption by employees of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed A7 B7 V. The disadvantage of the imidization catalyst described in (2) of the invention is that only organic ion exchangers have been proven to have heat and mechanical sensitivities as needed. To remedy the above shortcomings, in EP 〇449 089 proposed the use of acidic metal oxides, especially A 1 203, T i 02, S i 0 2 and Z r 0 2 as imidization catalysts and reactions in two separate reaction chambers, in 2 The imidization is carried out at 0 to 150 ° C and 15 to 200 bar, and the hydrogenation is carried out at 60 to 150 ° C and 50 to 300 bar. This method is found to form a very large number of hydroxyl groups. Amine, which is isophorone amino alcohol (= 3— Aminomethyl_.3,5,5_trimethylcyclohexanol) cis and trans isomers, so the purification step needs to be exhausted. When used according to DE patent application 195 40 191.3 special use Cobalt hydride catalyst (rene type) when manufacturing isophorone diamine, it proves that additional imidization catalyst is needed in order to minimize hydroxylamines and other unwanted secondary products. When combined with imine When the catalyst of the chemical catalyst and the cobalt hydrogenation catalyst reduces the imine group and the eye group, a very good yield and high-purity isophorone diamine can be obtained. EP — A 〇 6 2 3 585 also reveals the two-stage A method is provided for reducing aminated ketones such as isophorone. The imidization catalyst is activated carbon, and the hydrogenation catalyst is a cobalt catalyst containing alkaline earth metal carbonate and / or lanthanum oxide. It was found that the amount of catalyst was quite high relative to the converted (97.7%) isophorone, which led to the cost of the tritium reactor. Other disadvantages of this method were incomplete conversion and high pressure. According to DE — A 44 2 6 472 Even when using the paper on the carrier, the Chinese standard (CNS) A4 applies Specifications (: 210X297 mm) (Please read the note on the back before filling this page)
-5 - 經濟部中央標準局員工消費合作社印裂 A7 B7 五、發明説明（3 ) 的雜聚酸類.作爲亞胺化觸媒時，必須使用相對於轉化的異 佛爾酮腈之大量的亞胺化觸媒、高壓（2 3 8巴）以及相 當高的亞胺化溫度（7 0 °C ),因此由於減活化作用而有 限制觸媒使用壽命的風險。據此本.發明之目的是提供另一 種方法供還原性胺化含合氧基化合物，尤其是異佛爾酮睛 ，使用亞胺化觸媒及氫化觸媒，此方法不會顯現先前技藝 的缺點，具體地說，在亞胺化階段必須可在最低可能的反 應溫度下持續進行此方法，且在給定的觸媒量下，此方法 必須可提供較高的反應速率及較高的轉化率，且因此在粗 異佛爾酮二胺產物中比先前技藝系統有較低的羥基胺含量 〇 頃經發現一種從含合氧基化合物，其中可視需要再含 可還原的其他基團，製造一級及/或二級胺類的方.法，尤 其是從異佛爾酮睛製造異佛爾酮二胺，其中含合氧基化合 物是在形成亞胺的觸媒存在下，在或不在含供製造一級胺 類目的之過量氨或供製造二級胺類目的之較低量單烷基胺 之有機溶劑中亞胺化，且所得的反應產物用氫氣在氫化觸 媒存在下及2 0至2 5 0 °C的溫度範圍與〇. 5至20 MPa的壓力範圍下氫化，此方法的特徵是使用含磺酸鹽 基且不會部份或完全溶解在反應介質中的有機聚矽氧烷作 爲亞胺化觸媒。 附屬的專利申請範圍係關於本發明的較佳具體實施例 〇 根據本發明的方法可用於從含合氧基化合物，也就是 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 —-------- (請先閲讀背面之注意事項再填寫本頁) .、訂 -6 - A7 B7 五、發明説明（4 ) 一般的含羰基化合物，製造一級及/或二級胺類，此含合 氧基化合物可含一或多個羰基及額外的其他還原性基團例 如睛基或烯烴雙鍵，此方法較宜關於從脂族、環脂族芳 族及雜芳族醛類與酮類製造一級及/或二級胺類，其中氨 在此反應中作爲亞胺化試劑，低碳單烷基胺，尤其是（ C i至C 4 )烷基胺可作爲亞胺化試劑使用供製造二級胺類 ，根據本發明的方法特別適於從相當高分子量具有複雜結 構或多元官能基的羰基化合物製造一級單一及二胺類，這 種化合物在單階段還原性胺化反應中導致不滿意的空間/ 時間產量，形成不要的二級產物或損耗觸媒的活性，雖然 具有非常不同結構的含合氧基化合物可得自此方法，例如 苄基胺得自苄基醛，糠基胺得自糠醛且異佛爾酮二胺得自 異佛爾酮睛，使用從異佛爾酮睛工業化大量製造異佛爾酮 二胺的實例說明根據本發明的方法》 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 根據本發明使用的亞胺化觸媒較宜含美國專利4，5 52 ’ 700及5，354，831揭示的產物，在這些 產物中，磺酸鹽基係經由有機基連接至有機聚矽氧烷基質 ，在磺酸鹽基與有機聚矽氧烷基質間的有機基較宜爲含1 至12個碳原子的亞烴基，尤其是亞丙基，明確的參考文 獻可參見上述專利案關於適合作爲亞胺化觸媒的這類物質 之結構與可能的變化，一種特別較佳的觸媒實質上含化學 式單位 H03S — ( C Η 2 ) 3 — S i Ο3 / 2· a.S i 〇4/2 ，其中a爲4至2 0的整數，尤其是9，較佳觸媒的磺酸 含量較宜爲0. 5至1. 5mVal/克乾觸媒，尤其是 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 一 7 — A7 B7 五、發明説明（5 ) 〇 5至1.. OmVa 1/克，其中觸媒係用在固定床反 應器，此觸媒通常使用有形狀的形式，尤其是圓球形，實 質上含球形粒子的觸媒其直徑範圍較宜爲〇. 1至2毫米 ，製造此形狀觸媒的方法及其物質數據揭示在美國專利5 ，3 5 4，8 3 1，此形狀的粒子具有提升的孔洞體積； 此孔洞爲中型一及大型孔洞。 在亞胺化階段，使用的亞胺化觸媒可爲懸浮的觸媒或 排列在反應器內固定床形式，亞胺化觸媒以排列成固定床 形式較佳，進行反應的物質混合物可從底部添加，使反應 器保持在溢流的狀態，或從上面添加物質混合物以淋流的 方式操作反應器。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 可從亞胺化階段往下流至氫化階段使用的習知氫化觸 媒，爲一般已知供氫化亞胺類及供氫化視需要存在於含合 氧基化合物的其他還原性基團之觸媒，較佳的氫化觸媒係 選自含鈷、鎳、釕及/或其他稀有金屬的觸媒，這種觸媒 的實例揭示在上述提到的文獻中，使用的氫化觸媒也可爲 懸浮形式或固定床觸媒，當使用固定床觸媒進行氫化時， 淋流床的操作較宜。 亞胺化反應器中加入從合氧基化合物製備的物質混合 物供製造異佛爾酮二胺，即異佛爾酮腈、氨或當製造二級 胺時，單烷基胺與視需要使用的一或多種有機溶劑，使用 過量的氨及單烷基胺，合氧基化合物每個羰基的氨或單院 基胺莫耳比例範圍較宜爲約2及5 0，根據一較佳具體實 施例，添加至亞胺化反應器的物質混合物中也可含有機溶 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 8 - A7 ___ _^_B7____ 五、發明説明（6 ) 劑，例如尤其是醇或醚，其中甲醇特別適宜。 在進行亞胺化的溫度下，亞胺化觸媒不會被反應混合 物部份溶解，通常低於1 〇 0°c，此溫度較宜在〇至7 〇 °C的範圍，尤其是10至3 0 °C，此反應通常在密閉容器 建立的壓力下進行。 當製造異佛爾酮二胺時，添加至亞胺化反應器的物質 混合物較宜含甲醇及1 0至4 0重量％，尤其是1 0至 3 0重量％的異佛爾酮睛以及1 0至4 0重量％，尤其是 20至40重量％的氨，經由蒸餾法處理的異佛爾酮二胺 餾份可另外添加至此物質混合物中，其條件是此餾份含適 合形成異佛爾酮二胺的原料，爲了增加整體的產量，適宜 將沸點高於異佛爾酮二胺的餾份添加至亞胺化階段中，該 餾份除了異佛爾酮二胺殘留物外，還含3，3，5 —三甲 基-6 -亞胺基-7-疊氮二環-[3. 2. 1]辛烷之主 要產物，或者是此二級產物餾份也可添加至氫化階段中。 經濟部中央標準局員工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 將亞胺化階段流出的反應混合物或從其中製備而含亞 胺化產物的物質混合物添加至氫化階段，用本身已知的反 應情形進行氫化，反應溫度習知爲2 0至.2 5 0 °C，通常 高於5 0°C，氫化反應較宜在5 0至1 5 0°C進行，尤其 是在9 0至1 3 0°C，決定於使用的氫化觸媒，通常是在 0 5至25MPa的壓力下進行氫化，由其是在3至 10 MPa，通常氫化是存在或含至少一部分於亞胺化 階段中使用的氨或單烷基胺與溶劑下進行，用本身已知的 方法處理從氫化反應器流出的反應混合物，此處理通常包 本紙張又度適用中國國家標準（CNS ) A4規格（210X297公釐） ' ' 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（7 ) 括經由蒸緞去除氨或單烷基胺且隨後去除溶劑，並分餾粗 產物。 很訝異地，根據本發明使用的亞胺化觸媒之觸媒活性 ，比以含磺酸鹽基或酸性金屬氧化物的有機離子交換劑爲 基質之先前技藝觸媒的活性高出許多，其活性也高於在關 於二級產物的範圍下比其他先前技藝的亞胺化觸媒表現較 優的活性碳，根據本發明使用的亞胺化觸媒之其他優點是 具有延長的使用期限，而且不會降低下游氫化觸媒的活性 ，當從異佛爾酮腈製備異佛爾酮二胺時，另外證明經由使 '用根據本發明的亞胺化觸媒，與使用先前技藝的亞胺化觸 媒比較，可降低羥基胺類的含量，其主要是3—胺基甲基 —3，5，5 -三甲基環己醇的順式與反式異構物》 實例B 1及實例比較V B 1與V B 2 將2 0毫升1 8重量％甲醇系的異佛爾酮睛溶液與 2 0毫升3 0重量％氨水溶液在2 0°C下密閉的攪拌燒瓶 中摻混，加入4毫升亞胺化觸媒，經由U V偵測器測量異 佛爾酮腈濃度的下降》 將根據美國專利5，354，831製造的直徑 0.1至1. 4毫米高多孔性球形的含磺酸基有機聚矽氧 烷在B1中使用，此觸媒實質上含H03S — (CH2) 3 -S i Ο 3/ 2 · 9 S i 0 4/2的化學式單位且磺酸含量爲 0.9mVal/克乾觸媒。 在V B 1中的亞胺化觸媒爲以苯乙烯/二乙烯基苯爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 10 - --------©-0II (請先閲讀背面之注意事項再填寫本頁) ^4 —ί— I ϋϋ -s- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（8 ) 基質且含磺.酸鹽基的有機陽離子交換劑（Dow Chemicals 供應的 Dowex ® 5 0 W X 8 )。 在V B 2中的亞胺化觸媒爲活性碳（Nor it供應的 Nor i t RAX 1 )。 使用先前技藝的有機陽離子交換劑及活性碳時，在各 情形下轉化3 5%的異佛爾酮需要1 5分鐘以上，但是當 使用根據本發明含磺酸鹽基的有機聚矽氧烷時，只需 7. 5分鐘就可達到，因此根據本發明的亞胺化觸媒實質 上比先前技藝的亞胺化觸媒有更高的活性。 實例B2及實例比較VB3、 VB4、 VB5與VB6 在過量氨存在及用甲醇作爲溶劑下，在包括亞胺化反 應及下游氫化反應器的裝置內用氫氣使異佛爾酮睛胺化及 還原化》 使用的亞胺化反應器爲含15毫升亞胺化觸媒的試管 ，其中用幫浦從底部往上通入異佛爾酮睛、氨及甲醇的混 合物，亞胺化階段的溫度保持在2 5 °C。 亞胺化反應器中加入從反應器入口往上立即混合的混 合物，其係由5 2毫升/小時的起始溶液（2 4重量％異 佛爾酮腈與7 6重量％甲醇）與2 8毫升/小時的液態氨 製成，因此亞胺化反應器中的LHSV值爲5. 3小時 —1。 使用的氫化反應器爲以淋流床方式操作的試管並含 1 5 0毫升的氫化觸媒，使用高度5毫米且直徑3毫米的 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁)-5-A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The heteropoly acids of invention description (3). When used as imidization catalyst, a large amount of sub-acids relative to the converted isophoronenitrile must be used. Aminated catalysts, high pressure (2 38 bar), and fairly high imidization temperature (70 ° C), so there is a risk of limiting the life of the catalyst due to deactivation. Accordingly, the purpose of this invention is to provide another method for reductively aminated oxy-containing compounds, especially isophorone, using imidization catalysts and hydrogenation catalysts. This method does not show the previous technology Disadvantages, in particular, the process must be continued at the lowest possible reaction temperature during the imidization stage, and at a given amount of catalyst, the process must provide a higher reaction rate and higher conversion Yield, and therefore has a lower hydroxylamine content in the crude isophorone diamine product than the prior art system. He was found to be manufactured from a compound containing oxygenates, which may further contain other reducible groups, if necessary. Method for primary and / or secondary amines, especially isophorone diamine produced from isophorone eyes, wherein the oxygen-containing compound is in the presence or absence of an imine-containing catalyst Excess ammonia for the production of primary amines or a lower amount of monoalkylamine for the production of secondary amines is imidized in an organic solvent, and the resulting reaction product is hydrogenated in the presence of a hydrogenation catalyst and 20 to 2 5 0 ° C A pressure range of 5 to 20 MPa hydrogenation, this method is characterized by the use of organopolysiloxanes containing silicon oxide alkyl sulfonate group and does not partially or completely dissolved in the reaction medium as the imidization catalyst. The scope of the attached patent application relates to the preferred embodiments of the present invention. The method according to the present invention can be used for the compound containing oxygenates, that is, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm> — -------- (Please read the notes on the back before filling out this page). Order -6-A7 B7 V. Description of the invention (4) General carbonyl-containing compounds for the production of primary and / or secondary amines This type of oxygen-containing compound may contain one or more carbonyl groups and additional other reducing groups such as cyano or olefin double bonds. This method is more suitable for aliphatic, cycloaliphatic aromatic and heteroaromatic aldehydes. And ketones to produce primary and / or secondary amines, in which ammonia acts as an imidization reagent in this reaction, and low-carbon monoalkylamines, especially (Ci to C4) alkylamines can be used as imidization Reagents are used for the production of secondary amines. The method according to the invention is particularly suitable for the production of primary mono- and diamines from carbonyl compounds of relatively high molecular weight with complex structures or polyfunctional groups. Such compounds undergo reductive amination in a single stage. Lead to unsatisfactory space / hour Yield, formation of unwanted secondary products or loss of catalyst activity, although oxygenate-containing compounds with very different structures can be obtained from this process, for example benzylamine from benzylaldehyde, furfurylamine from furfural and different The phorone diamine is obtained from isophorone eye, and the example of industrial mass production of isophorone diamine from isophorone eye is used to illustrate the method according to the present invention. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please (Please read the notes on the back before filling this page)) The imidization catalyst used in accordance with the present invention preferably contains the products disclosed in U.S. Patent Nos. 4,5 52'700 and 5,354,831. Among these products, sulfonates The radical is connected to the organopolysiloxane by an organic group. The organic group between the sulfonate group and the organopolysiloxane is preferably an alkylene group containing 1 to 12 carbon atoms, especially a propylene group. For a clear reference, please refer to the above patents regarding the structure and possible changes of such substances suitable as imidization catalysts. A particularly preferred catalyst essentially contains the chemical formula unit H03S — (C Η 2) 3 — S i Ο3 / 2 · aS i 〇4 / 2, where a is an integer of 4 to 20, especially 9, the sulfonic acid content of the preferred catalyst is more preferably 0.5 to 1.5 mVal / g dry catalyst, especially the paper size applies to China National Standard (CNS) A4 specification (210X297 mm)-7-A7 B7 V. Description of the invention (5) 〇5 to 1 .. OmVa 1 / g, in which the catalyst is used in fixed bed reactor, this catalyst is usually Using shaped forms, especially round spheres, catalysts containing substantially spherical particles preferably have a diameter in the range of 0.1 to 2 mm. The method of manufacturing this shape catalyst and its material data are disclosed in US Patent 5,3 5 4, 8 3 1, the particles in this shape have a raised pore volume; the pores are medium-sized and large. In the imidization stage, the imidization catalyst used may be a suspended catalyst or a fixed bed arranged in the reactor. The imidization catalyst is preferably arranged in a fixed bed. Add at the bottom to keep the reactor in an overflow state, or add a substance mixture from above to operate the reactor in a trickle manner. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) The conventional hydrogenation catalysts that can flow down from the imidization stage to the hydrogenation stage are generally known for hydrogenated imine Catalysts for hydrogenation and other reducing groups present in the oxygen-containing compound as needed. Preferred hydrogenation catalysts are selected from catalysts containing cobalt, nickel, ruthenium and / or other rare metals. Examples of catalysts are disclosed in the above-mentioned literature. The hydrogenation catalysts used can also be suspended or fixed bed catalysts. When fixed bed catalysts are used for hydrogenation, the operation of the leaching bed is more suitable. The imidization reactor is charged with a mixture of substances prepared from oxygenated compounds for the production of isophorone diamine, that is, isophorone nitrile, ammonia or when making secondary amines, monoalkylamines and One or more organic solvents, using excess ammonia and monoalkylamines. The molar ratio of ammonia or monoamine amines per carbonyl group of the oxygen compound is preferably about 2 and 50, according to a preferred embodiment. The material mixture added to the imidization reactor may also contain organic solvents. The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm). 8-A7 ___ ___B7____ V. Description of the invention (6) Especially, for example, alcohols or ethers, with methanol being particularly suitable. The imidization catalyst will not be partially dissolved by the reaction mixture at the temperature at which the imidization is carried out, which is usually lower than 100 ° c, and this temperature is preferably in the range of 0 to 70 ° C, especially 10 to At 30 ° C, the reaction is usually carried out under pressure established in a closed container. When isophorone diamine is manufactured, the substance mixture added to the imidization reactor preferably contains methanol and 10 to 40% by weight, especially 10 to 30% by weight of isophorone and 1 0 to 40% by weight, especially 20 to 40% by weight of ammonia, an isophorone diamine fraction treated by distillation may be additionally added to the substance mixture, provided that this fraction contains isoforms In order to increase the overall yield of ketodiamine, it is suitable to add a fraction with a boiling point higher than that of isophoronediamine to the imidization stage. This fraction contains, in addition to the isophoronediamine residue, The main product of 3,3,5-trimethyl-6-imino-7-azidobicyclo- [3. 2.1] octane, or this secondary product fraction can also be added to the hydrogenation stage in. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Add the reaction mixture flowing out from the imidization stage or the substance mixture containing imidized products prepared from it to the hydrogenation stage, The hydrogenation is performed by a reaction situation known per se. The reaction temperature is conventionally 20 to .250 ° C, usually higher than 50 ° C. The hydrogenation reaction is preferably performed at 50 to 150 ° C, especially At 90 to 130 ° C, depending on the hydrogenation catalyst used, hydrogenation is usually performed at a pressure of 0 5 to 25 MPa, from 3 to 10 MPa, usually hydrogenation is present or contains at least a part of the The ammonia or monoalkylamine used in the amination stage is carried out under a solvent, and the reaction mixture flowing out of the hydrogenation reactor is treated by a method known per se. This treatment usually covers the paper and applies the Chinese National Standard (CNS) A4. (210X297 mm) '' A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (7) Includes the removal of ammonia or monoalkylamine via steaming and subsequent removal of the solvent, and fractionates the crude product. Surprisingly, the catalytic activity of the imidized catalyst used according to the present invention is much higher than that of the prior art catalysts based on organic ion exchangers containing sulfonate groups or acidic metal oxides. Its activity is also higher than that of activated carbons that perform better than other prior art imidization catalysts in the range of secondary products. The other advantage of the imidization catalysts used in accordance with the present invention is that it has an extended service life, Moreover, it does not reduce the activity of the downstream hydrogenation catalyst. When isophorone diamine is prepared from isophorone nitrile, it is additionally proved that the use of the imine catalyst according to the present invention and the use of the imine of the prior art Compared with the catalyst, it can reduce the content of hydroxylamines, which is mainly the cis and trans isomers of 3-aminomethyl-3,5,5-trimethylcyclohexanol. Example B 1 and Examples Comparison of VB 1 and VB 2 20 ml of a 18% by weight methanol-based isophorone solution and 20 ml of a 30% by weight aqueous ammonia solution were mixed in a closed stirred flask at 20 ° C, and 4 ml was added. Imidization catalyst, measuring isophoronenitrile concentration by UV detector Descend "will be made according to US Patent 5,354,831 with a diameter of 0.1 to 1.4 millimeters and highly porous spherical sulfonic acid-containing organopolysiloxanes for use in B1. This catalyst essentially contains H03S — (CH2) The chemical formula unit of 3 -S i Ο 3/2 · 9 S i 0 4/2 and the sulfonic acid content is 0.9 mVal / g dry catalyst. The imidization catalyst in VB 1 is based on styrene / divinylbenzene. Paper size is applicable to China National Standard (CNS) A4 (210X297 mm)-10--------- ©- 0II (Please read the precautions on the back before filling this page) ^ 4 —ί— I ϋϋ -s- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (8) Matrix and sulfonate. Organic cation exchanger (Dowex ® 50 WX 8 supplied by Dow Chemicals). The imidization catalyst in V B 2 is activated carbon (Norit RAX 1 supplied by Nor it). When using the prior art organic cation exchanger and activated carbon, it takes more than 15 minutes to convert 35% of isophorone in each case, but when using the sulfonate-containing organic polysiloxane according to the present invention It can be achieved in only 7.5 minutes, so the imidization catalyst according to the present invention has substantially higher activity than the imidization catalyst of the prior art. Example B2 and Example Comparison VB3, VB4, VB5, and VB6 in the presence of excess ammonia and using methanol as a solvent, hydrogenating the isophorone with a hydrogenation reactor in a device including an imidization reaction and a downstream hydrogenation reactor 》 The imidization reactor used is a test tube containing 15 ml of imidization catalyst, in which a mixture of isophorone, ammonia and methanol is passed from the bottom to the bottom. The temperature of the imidization stage is maintained at 2 5 ° C. The imidization reactor was charged with the mixture immediately mixed upward from the reactor inlet, which was composed of 5 2 ml / hour of starting solution (24% by weight of isophoronenitrile and 76% by weight of methanol) and 2 8 3 小时 -1。 Made from milliliter / hour of liquid ammonia, so the LHSV value in the imidization reactor is 5.3 hours—1. The hydrogenation reactor used is a test tube operated in a fluidized bed mode and contains 150 ml of hydrogenation catalyst. The paper size of 5 mm in height and 3 mm in diameter is applicable to the Chinese National Standard (CNS) A4 (210 X 297) Mm) (Please read the notes on the back before filling out this page)
a90B70 五、發明説明（9 ) 片劑之根據DE專利申請案43 45 265製造的雷內 型態活化鈷觸媒，氫化反應器的溫度保持在1 0 0°C且壓 力設定在6MP a，將流出亞胺化反應器的混合物與氫氣 共同加入氫化反應器中，調整氫氣流使全部的氫氣都被清 耗，分析從反應器流出的液體。 使用的亞胺化觸媒爲： B 2 :如同B 1之根據本發明的觸媒 VB3:Degussa供應壓出成型顆粒之二氧化鈦 P25 (直徑1毫米，高度3至4毫米） VB4:根據VB1之Dowex 50WX8陽離子交 換劑 VB 5 :押出成型的活性碳（直徑1毫米，高度3至4毫 米） VB6 :圓柱形片劑的無機離子交換劑沸石ZSM — 5 ( 高度及直徑爲約2毫米）。 經濟'那中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 根據從氫化反應器流出反應混合物的分析（使用內標 以G C測定），在下列表中說明羥基胺類相對於從異佛爾 酮睛形成的全部產物之比例，也就是說相對於實質上的異 佛爾酮二胺、兩種異構性羥基胺類（順式及反式- 3 -胺 基,,甲基一3，5，5 —三甲基環己醇）、3，5，5 —三 甲基一6—胺基一 7—疊氮二環[3. 2. 1]辛烷及2 — 疊氮—4，6，6 —三甲基二環[3. 2. 1 ]辛烷。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - A7 B7 390870 發明説明（1G ) 實例編號 -—一 羥基胺含量 B 2 1 . 0重量％ V B 3 4 . 0重量％ V B 4 3 . 6重量％ V B 5 1 . 6重量％ V B 6 8 . 5重量％ 五、 (請先閱讀背面之注意事項再填寫本頁) 當使用根據本發明的亞胺化觸媒時，由於在亞胺化階 段有較高的轉化率，所以羥基胺類的含量較低，同時也必 須強調其反應速率比活性碳高出很多，還觀察到使用沸石 γ及中度多孔性沸石MFI時，與VB6使用ZSM5相 同都形成大量的羥基胺類。 實例B 3及實例比較VB 7 經濟部中央標準局員工消費合作社印製 根據實例2的設備在其中敘述的情形下操作2 0 0小 時，其中在一情形下（ = B3)使用 B1中定義的根據 本發明之亞胺化觸媒，且在另一情形下（ = VB 7 )使用 活性碳。 即使在200小時後，B3中產物混合物的分析仍然 顯示相對於從異佛爾酮形成產物總量的1. 〇%羥基胺含 量，異佛爾酮二胺的產率爲94_ 8%至95. 〇%且在 個測試期間中保持固定。 V B 7中產物混合物的分析顯示羥基胺的比例在 本紙張尺度逋用中國國家標準（CNS ) A4規格（2!0X297公釐） -13 - S9GB70 五、發明説明（11 ) 200小時內從1. 6上升至2. 0%，而且從亞胺化反 應器流出的氫化觸媒之氫化活性明顯降低，異佛爾酮二胺 的產率在此期間從94. 3%下降1. 5%。 (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -14 -a90B70 V. Description of the invention (9) Tablets are manufactured in accordance with DE patent application 43 45 265 with Raine-type activated cobalt catalyst. The temperature of the hydrogenation reactor is maintained at 100 ° C and the pressure is set at 6MP a. The mixture flowing out of the imidization reactor was added to the hydrogenation reactor together with hydrogen, and the hydrogen flow was adjusted so that all the hydrogen was consumed, and the liquid flowing out of the reactor was analyzed. The imidization catalyst used is: B 2: The catalyst according to the present invention like B 1 VB3: Degussa supplies extruded particles of titanium dioxide P25 (diameter 1 mm, height 3 to 4 mm) VB4: Dowex according to VB1 50WX8 cation exchanger VB 5: Extruded activated carbon (1 mm in diameter, 3 to 4 mm in height) VB6: Inorganic ion exchanger zeolite ZSM-5 (about 2 mm in height and diameter) for cylindrical tablets. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the precautions on the back before filling out this page) Based on the analysis of the reaction mixture flowing out from the hydrogenation reactor (determined by GC using an internal standard), the following table describes the hydroxylamine Relative to the ratio of all products formed from isophorone eyes, that is, relative to substantially isophorone diamine, two isomeric hydroxyl amines (cis and trans-3 -amino groups, , Methyl-3,5,5-trimethylcyclohexanol), 3,5,5-trimethyl-6-amino-7-azidobicyclo [3. 2. 1] octane and 2 — Azide—4,6,6—trimethylbicyclo [3. 2. 1] octane. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -12-A7 B7 390870 Description of the invention (1G) Example number-Monohydroxyamine content B 2 1. 0% by weight VB 3 4. 0% by weight VB 4 3.6% by weight VB 5 1.6% by weight VB 68.5% by weight V. (Please read the notes on the back before filling out this page) When using the imidization catalyst according to the present invention, There is a high conversion rate in the imidization stage, so the content of hydroxyl amines is low. At the same time, it must be emphasized that the reaction rate is much higher than activated carbon. It is also observed that when using zeolite γ and moderately porous zeolite MFI, Same as VB6 using ZSM5, both form a large number of hydroxylamines. Example B 3 and comparison of examples VB 7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the device according to Example 2 was operated for 200 hours under the conditions described therein, of which in one case (= B3) the basis defined in B1 was used The imidization catalyst of the present invention, and in another case (= VB 7) activated carbon is used. Even after 200 hours, the analysis of the product mixture in B3 still showed a yield of 94-8% to 95.5% of isophorone diamine relative to the 1.0% hydroxylamine content of the total product formed from isophorone. 〇% and remained fixed during each test period. The analysis of the product mixture in VB 7 showed that the ratio of hydroxylamine was in accordance with the Chinese National Standard (CNS) A4 specification (2! 0X297 mm) -13-S9GB70 at the paper scale. 5. Description of the invention (11) Within 200 hours from 1. 6% to 2.0%, and the hydrogenation activity of the hydrogenation catalyst flowing from the imidization reactor was significantly reduced, and the yield of isophoronediamine decreased from 94.3% to 1.5% during this period. (Please read the precautions on the back before filling this page) Order Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -14-